US7880023B2 - 2-Nitratoethyl oxirane, poly (2-nitratoethyl oxirane) and preparation method thereof - Google Patents
2-Nitratoethyl oxirane, poly (2-nitratoethyl oxirane) and preparation method thereof Download PDFInfo
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- US7880023B2 US7880023B2 US12/431,754 US43175409A US7880023B2 US 7880023 B2 US7880023 B2 US 7880023B2 US 43175409 A US43175409 A US 43175409A US 7880023 B2 US7880023 B2 US 7880023B2
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- oxirane
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- nitratoethyl
- nitratoethyl oxirane
- pgn
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- KIACKBSBNZLPBI-UHFFFAOYSA-N 2-(oxiran-2-yl)ethyl nitrate Chemical compound [O-][N+](=O)OCCC1CO1 KIACKBSBNZLPBI-UHFFFAOYSA-N 0.000 title claims abstract description 18
- 238000002360 preparation method Methods 0.000 title abstract description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 9
- BTANRVKWQNVYAZ-UHFFFAOYSA-N 2-butanol Substances CCC(C)O BTANRVKWQNVYAZ-UHFFFAOYSA-N 0.000 claims description 7
- ARXKVVRQIIOZGF-UHFFFAOYSA-N 1,2,4-butanetriol Chemical compound OCCC(O)CO ARXKVVRQIIOZGF-UHFFFAOYSA-N 0.000 claims description 6
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 5
- 229910017604 nitric acid Inorganic materials 0.000 claims description 5
- 238000000034 method Methods 0.000 claims description 2
- -1 poly(2-nitratoethyl oxirane) Polymers 0.000 abstract description 19
- 239000011230 binding agent Substances 0.000 abstract description 12
- 230000015572 biosynthetic process Effects 0.000 abstract description 11
- 229920003225 polyurethane elastomer Polymers 0.000 abstract description 11
- 238000003786 synthesis reaction Methods 0.000 abstract description 11
- 239000000178 monomer Substances 0.000 abstract description 6
- 150000001875 compounds Chemical class 0.000 abstract description 5
- 239000002360 explosive Substances 0.000 abstract description 5
- 238000006116 polymerization reaction Methods 0.000 abstract description 4
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 24
- 238000006243 chemical reaction Methods 0.000 description 18
- 239000000243 solution Substances 0.000 description 12
- 239000000463 material Substances 0.000 description 7
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 5
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 5
- KZMGYPLQYOPHEL-UHFFFAOYSA-N Boron trifluoride etherate Chemical compound FB(F)F.CCOCC KZMGYPLQYOPHEL-UHFFFAOYSA-N 0.000 description 4
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 4
- WTEOIRVLGSZEPR-UHFFFAOYSA-N boron trifluoride Chemical compound FB(F)F WTEOIRVLGSZEPR-UHFFFAOYSA-N 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- 239000001257 hydrogen Substances 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- 239000011541 reaction mixture Substances 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- FKLJPTJMIBLJAV-UHFFFAOYSA-N Compound IV Chemical compound O1N=C(C)C=C1CCCCCCCOC1=CC=C(C=2OCCN=2)C=C1 FKLJPTJMIBLJAV-UHFFFAOYSA-N 0.000 description 3
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 3
- 229920002635 polyurethane Polymers 0.000 description 3
- 239000004814 polyurethane Substances 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 229910015900 BF3 Inorganic materials 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 229920002121 Hydroxyl-terminated polybutadiene Polymers 0.000 description 2
- VUITVQCTOICKLM-UHFFFAOYSA-N O=[N+]([O-])OCCC(O)COCCCCO.O=[N+]([O-])OCCC1CO1 Chemical compound O=[N+]([O-])OCCC(O)COCCCCO.O=[N+]([O-])OCCC1CO1 VUITVQCTOICKLM-UHFFFAOYSA-N 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 239000012047 saturated solution Substances 0.000 description 2
- 239000011780 sodium chloride Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- UEGSMSXVBSEFOW-UHFFFAOYSA-M CC(=O)OC(CCO[N+](=O)[O-])COP.O=[N+]([O-])OCCC(O)COP.[V]I Chemical compound CC(=O)OC(CCO[N+](=O)[O-])COP.O=[N+]([O-])OCCC(O)COP.[V]I UEGSMSXVBSEFOW-UHFFFAOYSA-M 0.000 description 1
- XYXKCNJXWICQDX-WAUWOPGMSA-N CC(=O)OC(COP)CO[N+](=O)[O-].O=C=O.O=[N+]([O-])OCC(O)COP.[H]/C(COP)=C(\[H])O[N+](=O)[O-].[H]C(O[N+](=O)[O-])C(COP)OC(C)=O Chemical compound CC(=O)OC(COP)CO[N+](=O)[O-].O=C=O.O=[N+]([O-])OCC(O)COP.[H]/C(COP)=C(\[H])O[N+](=O)[O-].[H]C(O[N+](=O)[O-])C(COP)OC(C)=O XYXKCNJXWICQDX-WAUWOPGMSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- CWPHDAPSFLXPPH-UHFFFAOYSA-L I.II.I[IH]I.O=[N+]([O-])O.O=[N+]([O-])OCCC(O)COCCCCO.O=[N+]([O-])OCCC(O)CO[N+](=O)[O-].O=[N+]([O-])OCCC1CO1.OCCC(O)CO.O[Na].[V]I Chemical compound I.II.I[IH]I.O=[N+]([O-])O.O=[N+]([O-])OCCC(O)COCCCCO.O=[N+]([O-])OCCC(O)CO[N+](=O)[O-].O=[N+]([O-])OCCC1CO1.OCCC(O)CO.O[Na].[V]I CWPHDAPSFLXPPH-UHFFFAOYSA-L 0.000 description 1
- JHLTZNAWPODORS-UHFFFAOYSA-N I.II.O=[N+]([O-])O.O=[N+]([O-])OCCC(O)CO[N+](=O)[O-].OCCC(O)CO Chemical compound I.II.O=[N+]([O-])O.O=[N+]([O-])OCCC(O)CO[N+](=O)[O-].OCCC(O)CO JHLTZNAWPODORS-UHFFFAOYSA-N 0.000 description 1
- DCJBIRZKBRPGGT-UHFFFAOYSA-M II.I[IH]I.O=[N+]([O-])OCCC(O)CO[N+](=O)[O-].O=[N+]([O-])OCCC1CO1.O[Na] Chemical compound II.I[IH]I.O=[N+]([O-])OCCC(O)CO[N+](=O)[O-].O=[N+]([O-])OCCC1CO1.O[Na] DCJBIRZKBRPGGT-UHFFFAOYSA-M 0.000 description 1
- WNPYGHFBVXZACZ-UHFFFAOYSA-M I[IH]I.O=[N+]([O-])OCCC(O)COCCCCO.O=[N+]([O-])OCCC1CO1.[V]I Chemical compound I[IH]I.O=[N+]([O-])OCCC(O)COCCCCO.O=[N+]([O-])OCCC1CO1.[V]I WNPYGHFBVXZACZ-UHFFFAOYSA-M 0.000 description 1
- NUSRQAACROHDGO-UHFFFAOYSA-N O=[N+]([O-])OCC(O)COCCCCO.O=[N+]([O-])OCC1CO1 Chemical compound O=[N+]([O-])OCC(O)COCCCCO.O=[N+]([O-])OCC1CO1 NUSRQAACROHDGO-UHFFFAOYSA-N 0.000 description 1
- UBKFBFJMXKBJGU-UHFFFAOYSA-N O=[N+]([O-])OCCC(O)COCCCCO Chemical compound O=[N+]([O-])OCCC(O)COCCCCO UBKFBFJMXKBJGU-UHFFFAOYSA-N 0.000 description 1
- VFCWGUWAMYMCGZ-UHFFFAOYSA-N O=[N+]([O-])OCCC(O)CO[N+](=O)[O-].OCCC(O)CO Chemical compound O=[N+]([O-])OCCC(O)CO[N+](=O)[O-].OCCC(O)CO VFCWGUWAMYMCGZ-UHFFFAOYSA-N 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000005457 ice water Substances 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- JOYRKODLDBILNP-UHFFFAOYSA-N urethane group Chemical group NC(=O)OCC JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D303/00—Compounds containing three-membered rings having one oxygen atom as the only ring hetero atom
- C07D303/02—Compounds containing oxirane rings
- C07D303/12—Compounds containing oxirane rings with hydrocarbon radicals, substituted by singly or doubly bound oxygen atoms
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D303/00—Compounds containing three-membered rings having one oxygen atom as the only ring hetero atom
- C07D303/02—Compounds containing oxirane rings
- C07D303/08—Compounds containing oxirane rings with hydrocarbon radicals, substituted by halogen atoms, nitro radicals or nitroso radicals
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
- C08G65/04—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers only
- C08G65/22—Cyclic ethers having at least one atom other than carbon and hydrogen outside the ring
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
- C08G65/26—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds
- C08G65/2603—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing oxygen
- C08G65/2606—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing oxygen containing hydroxyl groups
- C08G65/2609—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing oxygen containing hydroxyl groups containing aliphatic hydroxyl groups
Definitions
- the present invention relates to a synthesis of an energetic prepolymer used as a high-energy binder for an insensitive and high performance explosive.
- HTPB Hydroxyl-Terminated Polybutadiene
- FBX's Plastic-Bonded Explosives
- This binder is included in PBX in the amount of about 15% to improve mechanical properties of PBX's.
- this binder is, an inert material, and thereby causing reduction of energy of PBX's. Therefore, many efforts are made to develop a high-energy contained binder (an energetic binder) for increasing the energy of PBX's.
- PPN poly(glycidyl nitrate) expressed as the following formula 1 is a representative one.
- a monomer structure of the PGN is shown in following formula 2.
- reaction scheme 1 when the polyurethane elastomer is synthesized by using the PGN of Formula 1, hydrogen bonding to carbon to which a nitrate group bonds is chemically acidified thus to easily cause a decomposition reaction as shown in reaction scheme 1 thereby causing a decomposition of the main chain of polyurethane.
- the PGN has been known as a material having the best performance among existing energetic prepolymers, many researches are made in order to solve such problems. However, outstanding results have not been obtained yet.
- an object of the present invention is to provide a monomer, 2-nitratoethyl oxirane expressed as formula III, which has energy equal to PGN and an excellent storage stability, and poly(2-nitratoethyl oxirane) expressed as formula IV, which is polymerized therefrom.
- the present invention relates to a synthesis of an energetic prepolymer used as a high-energy binder for an insensitive and high performance explosive. More particularly, the present invention provides a novel compound, 2-nitratoethyl oxirane expressed as formula III and poly(2-nitratoethyl oxirane) expressed as formula IV, which is polymerized therefrom.
- 2-nitratoethyl oxirane of formula III is used as a monomer for a synthesis of poly(2-nitratoethyl oxirane) of formula IV.
- poly(2-nitratoethyl oxirane) of formula IV has a chemical structure similar to the PGN of formula 1 which is a prepolymer conventionally used as a high energy binder, and also shows performance as a high-energetic prepolymer similar to the PGN.
- the existing PGN is self-decomposed since hydrogen bonding to carbon to which a nitrate group bonds is unstable and a urethane group attacks the unstable hydrogen, thereby being rearranged.
- the compound IV in accordance with the present invention includes one more methylene group, whereby the unstable hydrogen is not spatially attacked by the polyurethane group, and thus the compound IV is not self-decomposed in a polyurethane elastomer. Accordingly, the compound IV is very useful as a high-energetic prepolymer capable of solving the problem in using the PGN.
- nitric acid is added to 1,2,4-butanetriol of the formula I and reacted at a room temperature.
- the reaction mixture is extracted with methylene chloride (MC), washed with water and dried. The solvent is removed to obtain 1,4-dinitrato-2-butanol of formula II (reaction scheme 3-1).
- reaction scheme 3-2 2-nitratoethyl oxirane of formula III
- poly(2-nitratoethyle oxirane) is equal to PGN, an existing energetic prepolymer, in an energy aspect but is not self-decomposed, which has been pointed out as a problem of the PGN. Accordingly, poly(2-nitratoethyl oxirane) is a very useful material as a new energetic prepolymer which is used as a high energy binder for an insensitive and high performance explosive.
- reaction mixture was extracted with 100 ml of methylene chloride. Then, the resulting material was washed three times with 150 ml of 10% sodium hydrogen carbonate, washed twice with 150 ml of a sodium chloride saturated solution, and dehydrated with anhydrous magnesium sulfate. Then, the solid was removed by filtering the solution, and volatile matter was removed by evacuating the solution for five hours at 10 mmHg/60° C., to obtain 39.9 g of 1,4-dinitrato-2-butanol (yield: 70%).
- reaction solution was extracted three times with 60 ml of methylene chloride.
- the resulting material was washed twice with 150 ml of sodium chloride saturated solution, and dehydrated with anhydrous magnesium sulfate.
- the obtained solution was filtered to remove the solid and then evacuated for five hours at 10 mmHg/60 ⁇ to completely remove volatile matter.
- the resulting product was purified using a Kuqelrohr distillation apparatus (Aldrich, Z40, 11405) to obtain 14.2 g of pure 2-nitratoethyl oxirane of formula III (yield: 52%).
- a yield of the obtained polymer was approximately 91%, a numeric average of the molecular weight 2, 380, a polydispersity 1.18, a hydroxyl group 0.586 eq/kg, a glass transition temperature ⁇ 43° C., and a thermal decomposition onset temperature 180° C.
- the compound of the present invention used as an energetic prepolymer or a monomer for preparation thereof can substitute for existing poly(glycidyl nitrate) (PGN) which has been known to be a promising one having the best performance among existing energetic prepolymers, but which has a problem to be self-decomposed after the synthesis of polyurethane elastomer, to solve this problem.
- PPN poly(glycidyl nitrate)
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Polyethers (AREA)
- Polyurethanes Or Polyureas (AREA)
Abstract
A synthesis of an energetic prepolymer used as a high-energy binder for an insensitive and high performance explosive is disclosed. More specifically, provided are a novel compound 2-nitratoethyl oxirane expressed by formula III, a novel compound poly(2-nitratoethyl oxirane) expressed by formula IV, obtained by polymerization of 2-nitratoethyl oxirane used as a monomer and a preparation method thereof. The compound, used as an energetic prepolymer and a monomer for preparation thereof can substitute for existing poly(glycidyl nitrate) (PGN) which has been known to be a promising one having the best performance among existing energetic prepolymers, but which has a problem to be self-decomposed after synthesis of polyurethane elastomer, to solve this problem.
Description
This application is a CONTINUATION of DIVISIONAL application Ser. No. 11/879,016, filed Jul. 12, 2007 now abandoned, which claims priority right of U.S. patent application Ser. No. 10/830,972, filed Apr. 22, 2004 (issued Oct. 30, 2007 as U.S. Pat. No. 7,288,681), which is entitled to priority of REPUBLIC OF KOREA patent application 27805/2003, filed Apr. 30, 2003.
1. Field of the Invention
The present invention relates to a synthesis of an energetic prepolymer used as a high-energy binder for an insensitive and high performance explosive.
2. Description of the Background Art
Currently, HTPB (Hydroxyl-Terminated Polybutadiene), a prepolymer for a binder for Plastic-Bonded Explosives (FBX's) is being widely used as a binder for polyurethane groups. This binder is included in PBX in the amount of about 15% to improve mechanical properties of PBX's. However, this binder is, an inert material, and thereby causing reduction of energy of PBX's. Therefore, many efforts are made to develop a high-energy contained binder (an energetic binder) for increasing the energy of PBX's. Among energetic binders developed as a result of such efforts, poly(glycidyl nitrate) (PGN) expressed as the following formula 1 is a representative one. A monomer structure of the PGN is shown in following formula 2.
However, as shown in following reaction scheme 1, after a polyurethane elastomer has been synthesized, the PGN of Formula 1 is self-decomposed in the polyurethane elastomer.
As shown in reaction scheme 1, when the polyurethane elastomer is synthesized by using the PGN of Formula 1, hydrogen bonding to carbon to which a nitrate group bonds is chemically acidified thus to easily cause a decomposition reaction as shown in reaction scheme 1 thereby causing a decomposition of the main chain of polyurethane. Nevertheless, since the PGN has been known as a material having the best performance among existing energetic prepolymers, many researches are made in order to solve such problems. However, outstanding results have not been obtained yet.
Therefore, an object of the present invention is to provide a monomer, 2-nitratoethyl oxirane expressed as formula III, which has energy equal to PGN and an excellent storage stability, and poly(2-nitratoethyl oxirane) expressed as formula IV, which is polymerized therefrom.
The foregoing and other objects, features, aspects and advantages of the present invention will become more apparent from the following detailed description of the present invention when taken in conjunction with the accompanying drawings.
Reference will now be made in detail to the preferred embodiments of the present invention, examples of which are illustrated in the accompanying drawings.
The present invention relates to a synthesis of an energetic prepolymer used as a high-energy binder for an insensitive and high performance explosive. More particularly, the present invention provides a novel compound, 2-nitratoethyl oxirane expressed as formula III and poly(2-nitratoethyl oxirane) expressed as formula IV, which is polymerized therefrom.
2-nitratoethyl oxirane of formula III is used as a monomer for a synthesis of poly(2-nitratoethyl oxirane) of formula IV. In addition, poly(2-nitratoethyl oxirane) of formula IV has a chemical structure similar to the PGN of formula 1 which is a prepolymer conventionally used as a high energy binder, and also shows performance as a high-energetic prepolymer similar to the PGN. As shown in reaction scheme 1, the existing PGN is self-decomposed since hydrogen bonding to carbon to which a nitrate group bonds is unstable and a urethane group attacks the unstable hydrogen, thereby being rearranged. However, unlike the existing PGN, as shown in following reaction scheme 2, the compound IV in accordance with the present invention includes one more methylene group, whereby the unstable hydrogen is not spatially attacked by the polyurethane group, and thus the compound IV is not self-decomposed in a polyurethane elastomer. Accordingly, the compound IV is very useful as a high-energetic prepolymer capable of solving the problem in using the PGN.
A synthesis of 2-nitratoethyl oxirane of formula III and a synthesis process of poly(2-nitraoethyl oxirane) of formula IV are shown in following reaction scheme 3.
Said reaction scheme will now be explained in more detail.
First, nitric acid is added to 1,2,4-butanetriol of the formula I and reacted at a room temperature. The reaction mixture is extracted with methylene chloride (MC), washed with water and dried. The solvent is removed to obtain 1,4-dinitrato-2-butanol of formula II (reaction scheme 3-1).
Then, sodium hydroxide is added to the obtained 1,4-dinitrato-2-butanol and reacted. The reaction mixture is extracted with MC, washed with water and dried. The solvent is removed, to obtain 2-nitratoethyl oxirane of formula III (reaction scheme 3-2).
Then, boron trifluoride (BF3) and 1,4-butandiol are reacted to the obtained 2-nitraoethyl oxirane of formula III and the polymerization thereof is performed to obtain poly(2-nitraoethyl oxirane) of formula IV (reaction scheme 3-3).
The obtained poly(2-nitratoethyle oxirane) is equal to PGN, an existing energetic prepolymer, in an energy aspect but is not self-decomposed, which has been pointed out as a problem of the PGN. Accordingly, poly(2-nitratoethyl oxirane) is a very useful material as a new energetic prepolymer which is used as a high energy binder for an insensitive and high performance explosive.
Hereinafter, the present invention will be described in more detail with reference to examples. However, the present invention is not limited by the following examples.
31.8 g (0.3 mol) of 1,2,4-butanetriol of formula I was put in a 3-neck flask of 250 ml equipped with a thermometer, a reflux condenser and a dropping funnel, and the temperature was controlled to be 0° C. or below. 100.2 g (1.59 mol) of 98% nitric acid was put in the dropping funnel, and the nitric acid was dropped to a solution, controlling the temperature of the reaction solution so as not to be over 10° C. After the nitric acid had been all dropped, the reaction mixture was left at a room temperature for about one hour to complete the reaction. Then, the obtained reaction solution was slowly added to 150 ml of ice water.
The reaction mixture was extracted with 100 ml of methylene chloride. Then, the resulting material was washed three times with 150 ml of 10% sodium hydrogen carbonate, washed twice with 150 ml of a sodium chloride saturated solution, and dehydrated with anhydrous magnesium sulfate. Then, the solid was removed by filtering the solution, and volatile matter was removed by evacuating the solution for five hours at 10 mmHg/60° C., to obtain 39.9 g of 1,4-dinitrato-2-butanol (yield: 70%).
NMR (CDCl3, δ for TMS): 4.40, 4.20 (m, 2H), 4.06 (m, 1H), 2.50, 2.19 (m, 2H)
9.9 g (0.205 mol) of 1,4-dinitrato-2-butanol obtained in example 1 was put in a 250 ml 3-neck flask and distilled water was added thereto. The temperature of a reaction solution was controlled to be 10° C. or below, then 24.6 g (0.306 mol) of 50% sodium hydroxide was injected thereto using a dropping funnel, controlling the temperature of the reaction solution so as not to be over 10° C. After the injection, a reaction was additionally made for three hours at a room temperature and completed.
Then, the reaction solution was extracted three times with 60 ml of methylene chloride. The resulting material was washed twice with 150 ml of sodium chloride saturated solution, and dehydrated with anhydrous magnesium sulfate. The obtained solution was filtered to remove the solid and then evacuated for five hours at 10 mmHg/60□ to completely remove volatile matter. In order to obtain pure 2-nitratoethyl oxirane which could be polymerized to a prepolymer, the resulting product was purified using a Kuqelrohr distillation apparatus (Aldrich, Z40, 11405) to obtain 14.2 g of pure 2-nitratoethyl oxirane of formula III (yield: 52%).
NMR (CDCl3, δ for TMS): 4.58 (t, 2H), 3.00 (m, 1H), 2.61, 2.53 (m, 2H), 2.03, 1.85 (m, 2H)
0.18 g (2 mol) of 1,4-butandiol was added to 0.28 g (2 mol) of boron trifluoride etherate (BF3OEt2) and evacuated for about two hours to completely remove ether. Then, 10 ml of methylene chloride was added thereto. A solution of 6.65 g (50 mol) of 2-nitratoethyl oxirane obtained in example 2 dissolved in methylene chloride was injected to the resulting solution for about three hours to perform polymerization. After polymerization, 50 ml of water and 30 ml of methylene chloride were additionally put therein for washing. Then, the resulting material was washed twice with 50 ml of saturated sodium chloride solution and dehydrated with anhydrous magnesium sulfate. 20 ml of ethanol was added to the obtained polymer and stirred to wash non-reaction organic matter. Then, volatile matter was completely removed by evacuating the resulting material for five hours at 1 mmHg/80□ to obtain polymer poly(2-nitratoethyl oxirane) expressed by formula IV.
A yield of the obtained polymer was approximately 91%, a numeric average of the molecular weight 2, 380, a polydispersity 1.18, a hydroxyl group 0.586 eq/kg, a glass transition temperature −43° C., and a thermal decomposition onset temperature 180° C.
After synthesizing a polyurethane elastomer with each of poly(2-nitratoethyl oxirane) obtained in a manner described in example 3 and existing poly(glycidyl nitrate) (PGN) by using N-100 curing agent, a change of hardness (Shore D hardness) was examined and the result was shown in the following table 1.
| TABLE 1 | ||
| Changes of hardness (shore D hardness) of | ||
| polyurethane elastomer formed by using poly(2-nitratoethyl oxirane) | ||
| and existing PGN over time | ||
| time | ||
| 15 | 30 | 3 | ||||||
| 3 days | 5 days | 7 days | 10 days | days | days | months | 6 months | |
| poly(2- | 2.0 | 3.0 | 3.5 | 3.5 | 3.5 | 3.5 | 3.6 | 3.6 |
| nitratoethyl | ||||||||
| oxirane) | ||||||||
| PGN | 2.0 | 3.0 | 2.5 | completely | — | — | — | — |
| decomposed | ||||||||
As shown in Table 1, in case of polyurethane elastomer formed by using an existing PGN, a polymer began decomposed from solid of gum-stock to liquid after about 1 week. However, in case of polyurethane elastomer formed by using poly(2-nitratoethyl oxirane) in accordance with the present invention, a physical property was maintained even after 6 months.
The compound of the present invention, used as an energetic prepolymer or a monomer for preparation thereof can substitute for existing poly(glycidyl nitrate) (PGN) which has been known to be a promising one having the best performance among existing energetic prepolymers, but which has a problem to be self-decomposed after the synthesis of polyurethane elastomer, to solve this problem.
As the present invention may be embodied in several forms without departing from the spirit or essential characteristics thereof, it should also be understood that the above-described embodiments are not limited by any of the details of the foregoing description, unless otherwise specified, but rather should be construed broadly within its spirit and scope as defined in the appended claims, and therefore all changes and modifications that fall within the metes and bounds of the claims, or equivalence of such metes and bounds are therefore intended to be embraced by the appended claims.
Claims (1)
1. A method for preparing 2-nitratoethyl oxirane expressed by formula III.
comprising the steps of:
reacting 1,2,4-butanetriol with nitric acid to obtain 1,4-dinitrato-2-butanol; and
treating the 1,4-dinitrato-2-butanol with sodium hydroxide to obtain 2-nitratoethyl oxirane.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US12/431,754 US7880023B2 (en) | 2003-04-30 | 2009-04-28 | 2-Nitratoethyl oxirane, poly (2-nitratoethyl oxirane) and preparation method thereof |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR10-2003-0027805A KR100514344B1 (en) | 2003-04-30 | 2003-04-30 | 2-nitratoethyl oxirane, poly(2-nitratoethyl oxirane) and preparation method thereof |
| KR10-2003-0027805 | 2003-04-30 | ||
| KR27805/2003 | 2003-04-30 | ||
| US11/879,016 US20080194852A1 (en) | 2003-04-30 | 2007-07-12 | 2-Nitratoethyl oxirane, poly(2-nitratoethyl oxirane) and preparation method thereof |
| US12/431,754 US7880023B2 (en) | 2003-04-30 | 2009-04-28 | 2-Nitratoethyl oxirane, poly (2-nitratoethyl oxirane) and preparation method thereof |
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| US11/879,016 Continuation US20080194852A1 (en) | 2003-04-30 | 2007-07-12 | 2-Nitratoethyl oxirane, poly(2-nitratoethyl oxirane) and preparation method thereof |
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| US20090275765A1 US20090275765A1 (en) | 2009-11-05 |
| US7880023B2 true US7880023B2 (en) | 2011-02-01 |
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| US11/879,016 Abandoned US20080194852A1 (en) | 2003-04-30 | 2007-07-12 | 2-Nitratoethyl oxirane, poly(2-nitratoethyl oxirane) and preparation method thereof |
| US12/431,754 Active US7880023B2 (en) | 2003-04-30 | 2009-04-28 | 2-Nitratoethyl oxirane, poly (2-nitratoethyl oxirane) and preparation method thereof |
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| US11/879,016 Abandoned US20080194852A1 (en) | 2003-04-30 | 2007-07-12 | 2-Nitratoethyl oxirane, poly(2-nitratoethyl oxirane) and preparation method thereof |
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| US7939489B2 (en) * | 2002-12-23 | 2011-05-10 | Avon Products, Inc. | Oil absorbent topical compositions and methods for using same |
| US20060089646A1 (en) * | 2004-10-26 | 2006-04-27 | Bonutti Peter M | Devices and methods for stabilizing tissue and implants |
| CN111925501A (en) * | 2020-07-21 | 2020-11-13 | 西安近代化学研究所 | PGN-based thermoplastic polyurethane elastomer containing Diels-Alder bond and one-pot preparation method |
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| GB8817545D0 (en) * | 1988-07-22 | 1988-08-24 | Secr Defence | Preparation of epoxy nitrates |
| US5162494A (en) * | 1990-11-05 | 1992-11-10 | Thiokol Corporation | Isotactic poly(glydicyl nitrate) and synthesis thereof |
| ES2051227B1 (en) * | 1992-07-31 | 1994-12-16 | Espanola Explosivos | PROCEDURE FOR THE OBTAINING OF A HYDROXYTHERMINATED POLYGLYCIDIL P-TOLUENSULFONATE POLYMER AND ITS APPLICATION IN THE SYNTHESIS OF EXPLOSIVE AND PHOTOSENSITIVE POLYMERS. |
| ES2051228B1 (en) * | 1992-07-31 | 1994-12-16 | Espanola Explosivos | PROCEDURE FOR THE OBTAINING OF HYDROXYTHERMINE POLYGLYCIDYLNITRATE AND ITS APPLICATION IN THE OBTAINING OF ENERGY POLYMERS. |
| AU1090301A (en) * | 1999-10-19 | 2001-04-30 | Alliant Techsystems Inc. | Polymerization of poly(glycidyl nitrate) from high purity glycidyl nitrate synthesized from glycerol |
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| KR100514344B1 (en) | 2005-09-13 |
| US7288681B2 (en) | 2007-10-30 |
| FR2854894A1 (en) | 2004-11-19 |
| US20050004374A1 (en) | 2005-01-06 |
| FR2854894B1 (en) | 2006-11-24 |
| KR20040093930A (en) | 2004-11-09 |
| US20090275765A1 (en) | 2009-11-05 |
| US20080194852A1 (en) | 2008-08-14 |
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